Polymerisation catalysts

ABSTRACT

A transition metal complex having the following Formula (A): wherein the monovalent groups R 1  and R 2  are —R a , —OR b , —NR c R d , and —NHR e : the monovalent groups R a , R b , R c , R d  and R e , and the divalent group R 3  are (i) aliphatic hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v) heterocyclic groups and (vi) heterosubstituted derivatives of said groups (i) to (v); M is a Group (3) to (11) or lanthanide metal; E is phosphorus or arsenic; X is an anionic group, L is a neutral donor group; n is (1) or (2), y and z are independently zero or integers, such that the number of X and L groups satisfy the valency and oxidation state of the metal M. n is preferably (2) and the two resulting R 1  groups are preferably linked. The complex can be used with optional activator to polymerise olefins.

The present invention relates to transition metal-based polymerisationcatalysts and to their use in the polymerisation and copolymerisation ofolefins.

The use of certain transition metal compounds to polymerise 1-olefins,for example, ethylene or propylene, is well established in the priorart. The use of Ziegler-Natta catalysts, for example, those catalystsproduced by activating titanium halides with organometallic compoundssuch as triethylaluminium, is fundamental to many commercial processesfor manufacturing polyolefins. Over the last three decades, advances inthe technology have led to the development of Ziegler-Natta catalystswhich have such high activities that olefin polymers and copolymerscontaining very low concentrations of residual catalyst can be produceddirectly in commercial polymerisation processes. The quantities ofresidual catalyst remaining in the produced polymer are so small as torender unnecessary their separation and removal for most commercialapplications. Such processes can be operated by polymerising themonomers in the gas phase, or in solution or in suspension in a liquidhydrocarbon diluent, or, in the case of propylene, in bulk.

Commodity polyethylenes are commercially produced in a variety ofdifferent types and grades. Homopolymerisation of ethylene withtransition metal based catalysts leads to the production of so-called“high density” grades of polyethylene. These polymers have relativelyhigh stiffness and are useful for making articles where inherentrigidity is required. Copolymerisation of ethylene with higher 1-olefins(eg butene, hexene or octene) is employed commercially to provide a widevariety of copolymers differing in density and in other importantphysical properties. Particularly important copolymers made bycopolymerising ethylene with higher 1-olefins using transition metalbased catalysts are the copolymers having a density in the range of 0.91to 0.93. These copolymers which are generally referred to in the art as“linear low density polyethylene” are in many respects similar to theso-called “low density” polyethylene produced by the high pressure freeradical catalysed polymerisation of ethylene. Such polymers andcopolymers are used extensively in the manufacture of flexible blownfilm.

Polypropylenes are also commercially produced in a variety of differenttypes and grades. Homopolymerisation of propylene with transition metalbased catalysts leads to the production of grades with a wide variety ofapplications. Copolymers of propylene with ethylene or terpolymers withethylene and higher 1-olefins are also useful materials.

In recent years the use of certain metallocene catalysts (for examplebiscyclopentadienylzirconiumdichloride activated with alumoxane) hasprovided catalysts with potentially high activity. Other derivatives ofmetallocenes have been shown to be potentially useful for producingpolypropylene with good activity, molecular weight and tacticitycontrol. However, metallocene catalysts of this type suffer from anumber of disadvantages, for example, high sensitivity to impuritieswhen used with commercially available monomers, diluents and process gasstreams, the need to use large quantities of expensive alumoxanes toachieve high activity, difficulties in putting the catalyst on to asuitable support and synthetic difficulties in the production of morecomplex catalyst structures suitable for polymerising propylene in atactic manner.

An object of the present invention is to provide a novel transitionmetal complex which can be used, optionally with an activator, forpolymerising unsaturated monomers. A further object of the presentinvention is to provide catalyst system and a process for polymerisingmonomers, for example, olefins, and especially for polymerising ethylenealone or propylene alone, or for copolymerising ethylene with higher1-olefins with high activity.

One aspect of the present invention provides a novel transition metalcomplex having the following Formula A:

wherein the monovalent groups R¹ and R² are independently selected from—R^(a), —OR^(b), —NR^(c)R^(d), and —NHR^(e):

-   the monovalent groups R^(a), R^(b), R^(c), R^(d), and R^(e), and the    divalent group R³ are independently selected from (i) aliphatic    hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatic    hydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v)    heterocyclic groups and (vi) heterosubstituted derivatives of said    groups (i) to (v);-   M is a metal from Group 3 to 11 of the Periodic Table or a    lanthanide metal; E is phosphorus or arsenic; X is an anionic group,    L is a neutral donor group; n is 1 or 2, y and z are independently    zero or integers such that the number of X and L groups satisfy the    valency and oxidation state of the metal M.

The monovalent groups R^(a), R^(b), R^(c), R^(d), and R^(e), and thedivalent group R³ are defined above as (i) aliphatic hydrocarbon, (ii)alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkylsubstituted aromatic hydrocarbon (v) heterocyclic groups, (vi)heterosubstituted derivatives of said groups (i) to (v). These definegroups preferably contain 1 to 30, more preferably 2 to 20, mostpreferably 2 to 12 carbon atoms. Examples of suitable monovalentaliphatic hydrocarbon groups are methyl, ethyl, ethenyl, butyl, hexyl,isopropyl and tert-butyl. Examples of suitable monovalent alicyclichydrocarbon groups are adamantyl, norbornyl, cyclopentyl and cyclohexyl.Examples of suitable monovalent aromatic hydrocarbon groups are phenyl,biphenyl, naphthyl, phenanthrenyl and anthacenyl. Examples of suitablemonovalent alkyl substituted aromatic hydrocarbon groups are benzyl,tolyl, mesityl, 2,6-diisopropylphenyl and 2,4,6-triisopropyl. Examplesof suitable monovalent heterocyclic groups are 2-pyridinyl, 3-pyridinyl,2-thiophenyl, 2-furanyl, 2-pyrrolyl, 2-quinolinyl. As regards thedivalent group R³, this, for example, can be selected from any of theaforementioned monovalent groups wherein one of the hydrogen atoms onthe said monovalent group is replaced by a valency bond to form thesecond bond on the divalent group R³.

Suitable substituents for forming heterosubstituted derivatives of saidgroups R^(a), R^(b), R^(c), R^(d), R^(e) and R³ are, for example,chloro, bromo, fluoro, iodo, nitro, amino, cyano, alkoxy, mercapto,hydroxyl and silyl. Examples of alkoxy groups are methoxy, ethoxy,phenoxy (i.e. —OC₆H₅), tolyloxy (i.e. —OC₆H₄(CH₃)), xylyloxy,mesityloxy. Examples of amino groups are dimethylamino, diethylamino,methylethylamino. Examples of mercapto groups are thiomethyl,thiophenyl. Examples of silyl groups are trimethylsilyl andtriethylsilyl. Examples of suitable heterosubstituted derivatives ofsaid groups (i) to (v) are 2-chloroethyl, 2-bromocyclohexyl,2-nitrophenyl, 4ethoxyphenyl, 4-chloro-2-pyridinyl,4-dimethylaminophenyl and 4-methylaminophenyl.

R¹ and R² can, if desired, form a single integral divalent group R⁴,wherein R⁴ is independently selected from the divalent groups —R^(a′)—,—O—R^(b′)—, —O—R^(b′)—O—, —N—(R^(c))R^(d′)—, —N(R^(c))—,—N(R^(c))—R^(d′)—N(R^(c))—, —Si(R^(c))₂—R^(a′)—Si(R^(c))₂—, and—Si(R^(c))₂—; and wherein the divalent groups R^(a′), R^(b′), and R^(d′)are independently selected from divalent (i) aliphatic hydrocarbon, (ii)alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkylsubstituted aromatic hydrocarbon (v) heterocyclic groups and (vi)heterosubstituted derivatives of said groups (i) to (v), and R^(c) is asdefined above.

Although R¹ and R² can form integral unit R⁴ it is preferred that theyare separate groups. Preferably R¹ and R² are separate, identicalgroups. Preferably, R¹ and R² are separate, identical aliphatichydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon or alkylsubstituted aromatic hydrocarbon groups.

When n=2, there are two phosphorus or arsenic-containing ligands on thetransition metal M. Under these circumstances there are two separate R¹groups (R^(1′) and R^(1″)) and two separate R² groups (R^(2′) andR^(2″)). It is preferred that at least one of the pairs of these groups,R^(1′) and R^(1″) or R²′ and R^(2″) are linked. For example, R^(1′) andR^(1″) can be linked to form R⁵ as illustrated in Formula B below.

The divalent group R⁵ is preferably selected from the divalent groupsrecited above for the divalent group R⁴.

Thus the present invention further provides a transition metal complexwherein n=2 and the R¹ groups on the two units

are linked to form R⁵ such that Formula A becomes Formula B below.

and wherein the divalent group R⁵ is selected from the divalent groups—R^(a′)—, —O—R^(b′)—, —O—R^(b′)—O—, —N—(R^(c))R^(d′)—,—N(R^(c))—R^(d′)—N(R^(c))—, —Si(R^(c))₂—R^(a′)—Si(R^(c))₂—, and—Si(R^(c))₂—; the divalent groups R^(a′), R^(b′), and R^(d′) beingindependently selected from divalent (i) aliphatic hydrocarbon, (ii)alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkylsubstituted aromatic hydrocarbon (v) heterocyclic groups and (vi)heterosubstituted derivatives of said groups (i) to (v).

M is preferably a Group 3 to 11 transition metal, more preferably Group5 to 7 transition metal. Most preferably M is vanadium. M can also be aGroup 3 to 6 transition metal.

Examples of groups suitably used as the divalent group R⁵ are —CH₂—,—CH₂CH₂—, —CH₂CH₂CH₂—, trans-1,2-cyclopentane, trans-1,2-cyclohexane,2,3-butane, 1,1′-biphenyl, 1,1′-binaphthyl, —N(Me)-, —N(Et)-,1,1′-biphenol and —Si(Me)₂-.

The divalent group R³ is defined above as independently selected from(i) aliphatic hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatichydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v)heterocyclic groups and (vi) heterosubstituted derivatives of saidgroups (i) to (v);. It is preferred that R³ is an alkyl substituted orheterosubstituted aromatic hydrocarbon group. More preferably R³ is analkyl substituted or heterosubstituted divalent 1,2-phenylene group. The1,2-phenylene group preferably has the said alkyl substitutuent orhetero atom in the position ortho to the ring-carbon atom bonded to theoxygen atom in Formula A. The 1,2-phenylene group is optionallysubstituted in one of more of the other remaining positions of the1,2-phenylene group.

When any of the defined monovalent groups R^(a), R^(b), R^(c), R^(d),and R^(e), and the divalent groups R^(a′), R^(b′), R^(d′), R³, R⁴, andR⁵ are heterocyclic, the atom or atoms present in the rings as theheteroatom can be, for example, oxygen, nitrogen, sulphur, phosphorus orsilicon.

E is preferably phosphorus.

M is a metal selected from Groups 3 to 11 of the Periodic table, morepreferably is selected from Groups 3 to 7. It can also be selected fromGroups 3 to 6. M is preferably vanadium.

The anionic group X can be, for example, a halide, preferably chlorideor bromide; or a hydrocarbyl group, for example, methyl, benzyl orphenyl; a carboxylate, for example, acetate or acetylacetate; an oxide;an amide, for example diethyl amide; an alkoxide, for example,methoxide, ethoxide or phenoxide; an acetylacetonate; or a hydroxyl. Or,for example, X can be a non-coordinating or weakly-coordinating anion,for example, tetrafluoroborate, a fluorinated aryl borate or a triflate.The anionic groups X may be the same or different and may independentlybe monoanionic, dianionic or trianionic.

The neutral donor group L can be, for example, a solvate molecule, forexample diethyl ether or THF (tetrahydrofuran); an amine, for example,diethyl amine, trimethylamine or pyridine; a phosphine, for exampletrimethyl phosphine or triphenyl phosphine; an olefin; water; aconjugated or non-conjugated diene.

The value of y in Formula A and B depends on the value of n, the chargeon the anionic group X and the oxidation state of the metal M. Forexample, if M is titanium in oxidation state +4 and n is 2, then y is 2if X is a monoanionic group (eg. chloride) or y is 1 if X is a dianionicgroup (eg. oxide); if M is titanium in oxidation state +4 and n is 1,then y is 3 if all X groups are monoanionic groups (eg. chloride) or yis 2 if one X group is a dianionic group (eg. oxide) and the other ismonoanionic. It is preferred that n is 2.

Particularly preferred complex compounds are those having the formulae

In the present invention the complex compounds having the Formula A andFormula B can be catalytically active by themselves, or may require theuse of an activator to render them sufficiently active for use incommercial polymerisation processes. Accordingly, the present inventionfurther comprises a catalyst system for the polymerisation ofunsaturated monomer comprising

(1) a complex compound having the Formula A or Formula B as hereinbeforedefined and optionally

(2) an activator compound.

The activator compound employed in the catalyst system of the presentinvention is suitably selected from organoaluminium compounds andorganoboron compounds. Suitable organoaluminium compounds includetrialky- or triaryl-aluminium compounds, for example,trimethylaluminium, triethylaluminium, tributylaluminium,tri-n-octylaluminium, ethylaluminium dichloride, diethylaluminiumchloride, methylaluminium dichloride, dimethylaluminium chloride,tris(pentafluorophenyl)aluminium and alumoxanes. Alumoxanes are wellknown in the art as typically the oligomeric compounds which can beprepared by the controlled addition of water to an alkylaluminiumcompound, for example trimethylaluminium. Such compounds can be linear,cyclic or mixtures thereof. Commercially available alumoxanes aregenerally believed to be mixtures of linear, cyclic and cage compounds.The cyclic alumoxanes can be represented by the formula [R¹⁶AlO]_(s) andthe linear alumoxanes by the formula R¹⁷(R¹⁸AlO)_(s) wherein s is anumber from about 2 to 50, and wherein R¹⁶, R¹⁷, and R¹⁸ representhydrocarbyl groups, preferably C₁ to C₆ alkyl groups, for examplemethyl, ethyl or butyl groups.

Examples of suitable organoboron compounds aredimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate,triphenylboron, dimethylphenylammonium tetra(pentafluorophenyl)borate,sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate,H⁺(OEt₂)[(bis-3,5-trifluoromethyl)phenyl]borate,trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl) boron.Mixtures of organoaluminium compounds and organoboron compounds may beused.

In the preparation of the catalysts of the present invention thequantity of activating compound selected from organoaluminium compoundsand organoboron compounds to be employed is easily determined by simpletesting, for example, by the preparation of small test samples which canbe used to polymerise small quantities of the monomer(s) and thus todetermine the activity of the produced catalyst. It is generally foundthat the quantity employed is sufficient to provide 0.1 to 20,000 atoms,preferably 1 to 2000 atoms of aluminium or boron per atom of M presentin the compound of Formula A or B.

EP1238989 discloses the use of activators (Lewis acids) selected from

-   -   (b-1) ionic-bonding compounds having a CdCl₂ type or a CdI₂ type        of layered crystal structure;    -   (b-2) clays, clay minerals, or ion-exchange layered compounds;    -   (b-3) heteropoly-compounds; and    -   (b-4) halogenated lanthanoid compounds.        The activator employed in the activated catalyst of the present        invention may be of the type disclosed in EP1238989 if desired.        Such Lewis acids are those compounds which capable of receiving        at least one electron pair and is capable of forming an ion pair        by reaction with the transition metal complex. The Lewis acid        includes the aforementioned (b-1) ionic-bonding compounds having        a layered crystal structure of a CdCl₂ type or CdI₂ type (b-2)        clay. clay minerals, or ion-exchange layered compounds, (b-3)        heteropoly compounds, and (b-4) halogenated lanthanoid        compounds. The Lewis acid further includes SiO₂, Al₂O₃, natural        and synthetic zeolites which have Lewis acid points formed by        heating or a like treatment, and complexes and mixtures thereof.

U.S. Pat. No. 6,399,535 discloses a coordinating catalyst system capableof polymerizing olefins comprising:

(I) as a pre-catalyst, at least one non-metallocene, non-constrainedgeometry, bidentate ligand containing transition metal compound ortridentate ligand containing transition metal compound capable of (A)being activated upon contact with the catalyst support-activatoragglomerate of (II) or (B) being converted, upon contact with anorganometallic compound, to an intermediate capable of being activatedupon contact with the catalyst support-activator agglomerate of (II),wherein the transition metal is at least one member selected from Groups3 to 10 of the Periodic table; in intimate contact with

(II) catalyst support-activator agglomerate comprising a composite of(A) at least one inorganic oxide component selected from SiO₂, Al₂O₃,MgO, AlPO₄, TiO₂, ZrO₂, and Cr₂O₃ and (B) at least one ion containinglayered material having interspaces between the layers and sufficientLewis acidity, when present within the catalyst support-activatoragglomerate, to activate the pre-catalyst when the pre-catalyst is incontact with the catalyst support-activator agglomerate, said layeredmaterial having a cationic component and an anionic component, whereinsaid cationic component is present within the interspaces of the layeredmaterial, said layered material being intimately associated with saidinorganic oxide component within the agglomerate in an amount sufficientto improve the activity of the coordinating catalyst system forpolymerizing ethylene monomer, expressed as Kg of polyethylene per gramof catalyst system per hour, relative to the activity of a correspondingcatalyst system employing the same pre-catalyst but in the absence ofeither Component A or B of the catalyst support-activator agglomerate;wherein the amounts of the pre-catalyst and catalyst support-activatoragglomerate which are in intimate contact are sufficient to provide aratio of micromoles of pre-catalyst to grams of catalystsupport-activator agglomerate of from about 5:1 to about 500:1. Thelayered material can be, for example, a smectite clay. The catalystsystem of the present invention can be employed with a catalystsupport-activator agglomerate as described in U.S. Pat. No. 6,399,535 ifdesired.

In addition to the activator compound, it can be advantageous to employcatalytic quantities of certain halogenated compounds that are capableof promoting catalyst activity. Promotors of this type are especiallyuseful in the case that the transition metal in the complex is vanadium.U.S. Pat. No.5,191,042 discloses that certain vanadium-based catalystsactivated with organoaluminium compounds can be promoted using a varietyof halogenated organic compounds, for example, carbon tetrachloride,hexachloroethylene, benzylbromide, benzylchloride and 2,3- or1,3-dichloropropylene. Other examples of halogenated organic compoundsthat can be used in this manner are ethyl trichloroacetate, chloroform(CHCl₃) and n-butylchloride. U.S. Pat. No.5,191,042 also refers to thedisclosure of Cooper (T. A Cooper, Journ; Am. Chem. Soc., 4158 (1973),which defines in Table 1 an organic halide activity index based on theability of the halide to oxidize certain vanadium compounds understandard conditions. For example, carbon tetrachloride is assigned areactivity of 1 in tetrahydrofuran at 20° C., and other listedhalogenated organic compounds have reactivities of from about 0.02 togreater than 200 relative to carbon tetrachloride. When it is desired touse a halogenated promotor, it is preferred to use those having a CooperIndex ranging from about 0.01 up to about 30. The use of such promoters,especially in combination with vanadium-based catalysts is generallywell known in the art, and for details of use of the such promotersreference may be made to U.S. Pat. No. 5,191,042 and to other prior artin this field. In the present invention it is possible to employ anyhalogenated organic compound as a promoter, but the compounds mentionedabove are preferred.

The catalyst of the present invention can, if desired, be utilised on asupport material. Suitable support materials are, for example, silica,alumina, or zirconia, magnesia, magnesium chloride or a polymer orprepolymer, for example polyethylene, polystyrene, orpoly(aminostyrene).

The following are examples of transition metal complexes that can beemployed as the catalyst of the present invention, or as the transitionmetal component of the catalysts system of the present invention:

The catalyst or catalyst system of the present invention can if desiredcomprise more than one of the define transition metal compounds.

In addition to said one or more defined transition metal compounds, thecatalyst or catalyst system of the present invention can also includeone or more other types of transition metal compounds or catalysts, forexample, transition metal compounds of the type used in conventionalZiegler-Natta catalyst systems, metallocene-based catalysts, or heatactivated supported chromium oxide catalysts (e.g. Phillips-typecatalyst). The catalyst or catalyst system of the present invention canalso used in conjunction with other catalysts producing only 1-olefins,either inside or outside the polymerisation reactor, and in this waymake copolymers of ethylene or propylene and these 1-olefins. Suitablecatalysts for producing 1-olefins may produce only 1-butene, only1-hexene or a distribution (for example, a Schulz-Flory distribution) of1-olefins.

If desired, the catalyst or catalyst system can be formed in situ in thepresence of the support material, or the support material can bepre-impregnated or premixed, simultaneously or sequentially, with one ormore of the catalyst components. The catalyst and catalyst system of thepresent invention can if desired be supported on a heterogeneouscatalyst, for example, a magnesium halide supported Ziegler Nattacatalyst, a Phillips type (chromium oxide) supported catalyst or asupported metallocene catalyst. Formation of the supported catalyst canbe achieved for example by treating the transition metal compounds ofthe present invention with alumoxane in a suitable inert diluent, forexample a volatile hydrocarbon, slurrying a particulate support materialwith the product and evaporating the volatile diluent. The producedsupported catalyst is preferably in the form of a free-flowing powder.The quantity of support material employed can vary widely, for examplefrom 100,000 to 1 grams per gram of metal present in the transitionmetal compound.

The present invention further provides a process for the polymerisationand copolymerisation of 1-olefins,.cycloolefins or dienes comprisingcontacting the monomeric olefin under polymerisation conditions with thepolymerisation catalyst of the present invention.

Suitable monomers for use in making homopolymers using thepolymerisation process of the of the present invention are, for example,ethylene, propylene, butene, hexene, and styrene. Preferred monomers areethylene and propylene.

Suitable monomers for use in making copolymers using the polymerisationprocess of the present invention are ethylene, propylene, 1-butene,1-hexene, 4-methylpentene-1, 1-octene, methyl methacrylate, methylacrylate, butyl acrylate, acrylonitrile, vinyl acetate, vinyl chloride,styrene and dienes, such as butadiene or hexadiene and cycloolefins,such as norbornene.

A particularly preferred process in accordance with the presentinvention is the copolymerisation of ethylene and or propylene withcomonomers selected from 1-olefins, acrylic acid esters, vinyl estersand vinyl aromatic compounds. Examples of suitable comonomers are1-butene, 1-hexene, 4-methylpentene-1, methyl methacrylate, methylacrylate, butyl acrylate, acrylonitrile, vinyl acetate, and styrene.

Preferred polymerisation processes are the homopolymerisation ofethylene or the homopolymerisation of propylene or copolymerisation ofethylene with one or more of propylene, butene, hexane-1 and4-methylpentene-1.

Also preferred is a process for the copolymerisation of ethylene and orpropylene with comonomers selected from 1-butene, 1-hexene,4-methylpentene-1, methyl methacrylate, methyl acrylate, butyl acrylate,acrylonitrile, vinyl acetate, and styrene, diene, cyclic olefin,norbornene and substituted norbornene.

The polymerisation conditions can be, for example, bulk phase, solutionphase, slurry phase or gas phase. If desired, the catalyst can be usedto polymerise ethylene under high pressure/high temperature processconditions wherein the polymeric material forms as a melt insupercritical ethylene. Preferably the polymerisation is conducted undergas phase fluidised or stirred bed conditions.

Slurry phase polymerisation conditions or gas phase polymerisationconditions are particularly useful for the production of high-densitygrades of polyethylene. In these processes the polymerisation conditionscan be batch, continuous or semi-continuous. In the slurry phase processand the gas phase process, the catalyst is generally fed to thepolymerisation zone in the form of a particulate solid. This solid canbe, for example, an undiluted solid catalyst system formed from thecomplex of Formula A or B and an activator, or can be the solid complexalone. In the latter situation, the activator can be fed to thepolymerisation zone, for example as a solution, separately from ortogether with the solid complex. Preferably the catalyst system or thetransition metal complex component of the catalyst system employed inthe slurry polymerisation and gas phase polymerisation is supported on asupport material. Most preferably the catalyst system is supported on asupport material prior to its introduction into the polymerisation zone.Suitable support materials are, for example, magnesium chloride, silica,alumina, zirconia, talc, kieselguhr, or magnesia. Impregnation of thesupport material can be carried out by conventional techniques, forexample, by forming a solution or suspension of the catalyst componentsin a suitable diluent or solvent, and slurrying the support materialtherewith. The support material thus impregnated with catalyst can thenbe separated from the diluent for example, by filtration or evaporationtechniques.

In the slurry phase polymerisation process the solid particles ofcatalyst, or supported catalyst, are fed to a polymerisation zone eitheras dry powder or as a slurry in the polymerisation diluent. Preferablythe particles are fed to a polymerisation zone as a suspension in thepolymerisation diluent. The polymerisation zone can be, for example, anautoclave or similar reaction vessel, or a continuous loop reactor, egof the type well know in the manufacture of polyethylene by the PhillipsProcess. When the polymerisation process of the present invention iscarried out under slurry conditions the polymerisation is preferablycarried out at a temperature above 0° C., most preferably above 15° C.The polymerisation temperature is preferably maintained below thetemperature at which the polymer commences to soften or sinter in thepresence of the polymerisation diluent. If the temperature is allowed togo above the latter temperature, fouling of the reactor can occur.Adjustment of the polymerisation within these defined temperature rangescan provide a useful means of controlling the average molecular weightof the produced polymer. A further useful means of controlling themolecular weight is to conduct the polymerisation in the presence ofhydrogen gas which acts as chain transfer agent. Generally, the higherthe concentration of hydrogen employed, the lower the average molecularweight of the produced polymer.

The use of hydrogen gas as a means of controlling the average molecularweight of the polymer or copolymer applies generally to thepolymerisation process of the present invention. For example, hydrogencan be used to reduce the average molecular weight of polymers orcopolymers prepared using gas phase, slurry phase or solution phasepolymerisation conditions. The quantity of hydrogen gas to be employedto give the desired average molecular weight can be determined by simple“trial and error” polymerisation tests.

Methods for operating gas phase polymerisation processes are well knownin the art. Such methods generally involve agitating (e.g. by stirring,vibrating or fluidising) a bed of catalyst, or a bed of the targetpolymer (i.e. polymer having the same or similar physical properties tothat which it is desired to make in the polymerisation process)containing a catalyst, and feeding thereto a stream of monomer at leastpartially in the gaseous phase, under conditions such that at least partof the monomer polymerises in contact with the catalyst in the bed. Thebed is generally cooled by the addition of cool gas (e.g. recycledgaseous monomer) and/or volatile liquid (e.g. a volatile inerthydrocarbon, or gaseous monomer which has been condensed to form aliquid). The polymer produced in, and isolated from, gas phase processesforms directly a solid in the polymerisation zone and is free from, orsubstantially free from liquid. As is well known to those skilled in theart, if any liquid is allowed to enter the polymerisation zone of a gasphase polymerisation process the quantity of liquid is small in relationto the quantity of polymer present in the polymerisation zone. This isin contrast to “solution phase” processes wherein the polymer is formeddissolved in a solvent, and “slurry phase” processes wherein the polymerforms as a suspension in a liquid diluent.

The gas phase process can be operated under batch, semi-batch, orso-called “continuous” conditions. It is preferred to operate underconditions such that monomer is continuously recycled to an agitatedpolymerisation zone containing polymerisation catalyst, make-up monomerbeing provided to replace polymerised monomer, and continuously orintermittently withdrawing produced polymer from the polymerisation zoneat a rate comparable to the rate of formation of the polymer, freshcatalyst being added to the polymerisation zone to replace the catalystwithdrawn form the polymerisation zone with the produced polymer.

In the polymerisation process of the present invention the processconditions are preferably gas phase fluidised or stirred bedpolymerisation conditions.

When using the catalysts of the present invention under gas phasepolymerisation conditions, the catalyst, or one or more of thecomponents employed to form the catalyst can, for example, be introducedinto the polymerisation reaction zone in liquid form, for example, as asolution in an inert liquid diluent. Thus, for example, the transitionmetal component, or the activator component, or both of these componentscan be dissolved or slurried in a liquid diluent and fed to thepolymerisation zone. Under these circumstances it is preferred theliquid containing the component(s) is sprayed as fine droplets into thepolymerisation zone. The droplet diameter is preferably within the range1 to 1000 microns. EP-A-0593083, the teaching of which is herebyincorporated into this specification, discloses a process forintroducing a polymerisation catalyst into a gas phase polymerisation.The methods disclosed in EP-A-0593,083 can be suitably employed in thepolymerisation process of the present invention if desired.

The present invention further provides novel compound having the FormulaC, suitable for forming a transition metal complex

wherein R³, R², R⁵ and E are as defined above and R²⁰ and R²¹ aremonovalent groups as defined for R² or hydrogen.

Preferably the ligand has the formula:

In a further embodiment of the present invention there is provided aprocess for the preparation of a catalytically active species comprisingreacting together

(a) a ligand having the Formula C

(b) a transition metal compound M(L)_(n) and optionally

(c) an activator

wherein R³, R², R⁵ and E are as defined above and R²⁰ and R²¹ aremonovalent groups as defined for R² or hydrogen, the transition metal Mis selected from Groups 3 to 11, preferably vanadium, L is independentlyselected from halide (for example F, Cl, Br, I), alkyl, substitutedallyl, cycloalkyl, substituted cycloalkyl; heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno,phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates,carbonates, nitrates, sulphates, ethers, thioethers and combinationsthereof; and neutral donor group, for example, ethers, amines,thioethers, phosphines and the like, optionally two or more-L groups maybe linked together in a ring structure and n is 1, 2, 3, 4, 5, or 6.

The activator can be any of the activators described throughout thisspecification. The reaction is preferably conducted in a hydrocarbonsolvent. The catalytic species can be used to polymerise monomers in themanner described above for the catalyst of the present invention.

The invention is further illustrated with reference to the followingExamples. In the Examples all manipulations of air/moisture-sensitivematerials were performed on a conventional vacuum/inert atmosphere(nitrogen) line using standard Schlenk line techniques, or in an inertatmosphere glove box.

EXAMPLE 1 Catalyst Synthesis EXAMPLE 1a Synthesis of 1-tert.butyl-2-(methoxymethoxy)benzene

The following reaction was carried out in an efficient fume cupboard. Toa rapidly stirred and cooled (0° C.) suspension of Na (5.52 g, 240 mmol)in dry THF (80 ml) under a nitrogen atmosphere was slowly added2-tert-butylphenol (38.8 ml, 200 mmol). The suspension was stirred atroom temperature for 3 h and the green solution filtered into a two-neckflask fitted with a reflux condenser. Separately, acetyl chloride (21.98g, 280 mmol) was added very slowly to dimethoxymethane (22.83 g, 300mmol) containing ZnCl₂ (50 mg) at 0° C. under a nitrogen atmosphere. Themixture was then stirred at room temperature for 1.5 h to givemethoxychloromethane, which was added portion-wise to the solution ofdeprotonated alcohol. The mixture was stirred at room temperature for 1h during which a white precipitate formed. The reaction was thenquenched with water (100 ml) and diluted with EtOAc (50 ml). The organiclayer was separated and washed with 1M NaOH (2×75 ml), 3M NaCl (1×100ml), dried (MgSO₄), filtered, and the solvent removed under vacuumovernight giving crude 1-tertbutyl-2-(methoxymethoxy)benzene as a yellowliquid. The product was further purified by column chromatography[alumina (neutral, +3% H₂O); hexane] (33.41 g, 172 mmol, 86% yield). ¹HNMR (CDCl₃): δ 7.35-6.65 (m, 4H, Ar—H), 5.27 (s, 2H, OCH₂O), 3.54 (s,3H, OCH₃), 1.43 (s, 9H, C(CH₃)₃).

EXAMPLE 1b Synthesis of2-tertbutyl-6-(diphenylphosphino)phenol—(“Compound 1”)

To a slurry of 1-tert-butyl-2-(methoxymethoxy)benzene (9.714 g, 50 mmol)in ether (50 ml) was added n-butyllithium (2.5M in hexanes, 20 ml, 50mmol) and the mixture stirred for 12 h. Chlorodiphenylphosphine (10.8ml, 60 mmol) was added to the solution dropwise at −78° C. The mixturewas then stirred at room temperature for 2 h. Degassed 2M HCl (50 ml)was added followed by degassed water (150 ml) and ether (100 ml). Thelayers were separated and the solvent removed from the organic fraction.The crude yellow oil was dissolved in THF (50 ml) and 5M HCl (50 ml)added. The mixture was stirred and heated at 50° C. for 3 h. Aftercooling, ether (30 ml) and water (100 ml) added giving a whiteprecipitate of HCl. This precipitate was collected by filtration,slurried with THF (75 ml) and aqueous ammonia (100 ml) slowly added. Thelayers were separated and the organic fraction further washed withaqueous ammonia (3×50 ml), brine (75 ml) and dried over Na₂SO₄. Thesolution was filtered and the solvent removed to give a thick oil. Thiswas further purified by column chromatography [alumina (neutral, +3%H₂O); hexane] to give (“Compound 1”) as a thick oil (10.533 g, 32 mmol,63% yield). Micro Anal. Calcd for C₂₂H₂₃OP: C, 79.02; H, 6.93. Found: C,78.90; H, 6.81. ¹H NMR (C₆D₆): δ 7.32-7.22 (several m, 5H, Ar—H),7.02-6.95 (several m, 7H, Ar—H) 6.72 (t, 1H, ³J(H)=7.6 Hz, Ar—H) 1.50(s, 9H, C(CH)₃). ¹³C{¹H} NMR (C₆D₆): δ 158.9 (d, ²J(PC)=20 Hz, Ar—C,),136.5, 135.6, 133.7, 133.5, 133.0, 129.6, 129.1, 129.0, 128.8, 121.5,120.1 (Ar—C), 35.2 (C(CH)₃), 29.8 (C(CH)₃). ³¹P{¹H} NMR (C₆D₆): δ −32.5(s). MS (m/z): 334 [M]⁺.

EXAMPLE 1c Synthesis of Sodium1-tertbutyl-3-(diphenylphosphino)phenoxide.THF (hereinafter “the Naderivative of Ligand 1”)

THF (50 ml) was added to a mixture of (Compound 1) (4.11 g, 12.3 mmol)and NaH (1.08 g, 45 mmol). The resultant slurry was stirred at 60° C.for 12 h. After cooling to room temperature the solution was filteredand the excess NaH washed with THF (20 ml). The THF solution was reducedin volume to around 15 ml and heptane (60 ml) added giving whitecrystals that formed over 12 h at room temperature. The crystals werefiltered, washed with pentane (2×20 ml) and dried under vacuum to givethe Na derivative of Ligand 1 (3.58 g, 8.35 mmol, 68% yield). Anal.Calcd for C₂₆H₃₀O₂PNa: C, 72.88; H, 7.06. Found: C, 72.96; H, 6.97. ¹HNMR (C₆D₆): δ 7.52-7.44 (m, 5H, PC₆H₅+C₆H₃), 7.15-7.04 (m, 6H, PC₆H₅),6.82-6.76 (m, 1H, C₆H₃), 6.63-6.57 (m, 1H, C₆H₃), 3.17-3.12 (m, 4H,OCH₂CH₂), 1.64 (s, 9H, C(CH₃)₃), 1.21-1.13 (m, 4H, OCH₂CH₂). ¹³C{¹H} NMR(C₆D₆): δ171.0 (d, ²J(PC) 17 Hz, Ar—C), 139.1 (d, ³J(PC)=6 Hz, Ar—C),136.6 (Ar—C), 134.0 (d,²J(PC)=18 Hz, Ar—C), 130.7 (Ar—C), 127.4 (d,¹J(PC)=24 Hz, Ar—C), 122.7 (d, ²J(PC)=17 Hz, Ar—C), 112.3 (Ar—C), 67.6(CH₂CH₂O), 34.8 (C(CH₃)), 30.0 (C(CH₃)), 25.0 (CH₂CH₂O). ³¹P{¹H} NMR(C₆D₆): δ −17.8 (s).

EXAMPLE 2 Synthesis of (Ligand 1)₂MCl₂ (M=Ti, Zr)—General Procedure

A solution of the Na derivative of Ligand 1 (2 equivalents) in THF wastransferred to a solution MCl₄(THF)₂ (1 eq.) in THF and stirred at roomtemperature for 12 h. The solvent was removed and the residue extractedwith dichloromethane (2×20 ml). Removing the solvent gave an orangeprecipitate that was washed with pentane (20 ml) and dried under vacuumto give the complex.

EXAMPLE 2a Synthesis of (Ligand 1)₂TiCl₂, (“Complex 1A”)

Reaction of the Na derivative of Ligand 1 (0.428 g, 1 mmol) andTiCl₄(THF)₂ (0.167 g, 0.5 mmol) gave the complex (Complex 1A) as anorange solid (0.357 g, 0.45 mmol, 91% yield). ¹H NMR (C₆D₆): δ 8.07-7.98(br t, 2H, Ar—H), 7.65-7.62 (br t, 2H, Ar—H), 7.30-7.21 (m, 3H, Ar—H),7.03-6.65 (m, 19H, Ar—H), 1.67 (s, 9H, C(CH₃)₃), 1.26 (s, 9H, C(CH₃)₃).³¹P{¹H} NMR (C₆D₆): δ 11.9 (s), 9.5 (s).

EXAMPLE 2b Synthesis of (Ligand 1)₂ZrCl₂; (“Complex 1B”)

Reaction of the Na derivative of Ligand 1 (2.142 g, 5.0 mmol) andZrCl₄(THF)₂ (0.943 g, 2.5 mmol) gave (Complex 1B) (1.816 g, 2.2 mmol,88% yield). ¹H NMR (C6D₆): δ 7.32-7.25 (br+m, 8H, Ar—H), 7.00-6.66 (m,16H, Ar—H), 1.46 (s, 18H, C(CH₃)₃). ³¹P{¹H} NMR (C₆D₆): δ −1.6 (s).

EXAMPLE 3 Ethylene polymerization using Complexes 1A and 1—GeneralProcedure

Polymerisations were performed by adding 5μM of the Complex(pre-catalyst) (in 5 ml toluene solution) to 100 ml toluene containing500 eq MAO under 2 bar ethylene pressure at 25° C. Polymerisations wererun for 30 min and terminated by addition of 10% HCl/MeOH. Insolubrepolymer was isolated by addition of 300 ml MeOH, filtration and washingwith MeOH.

EXAMPLE 3a

Ethylene polymerisation with Complex 1A. Following the above procedureyielded 2.0 g of polyethylene, corresponding to an activity of 390mmol⁻¹h⁻¹bar⁻¹.

EXAMPLE 3b

Ethylene polymerisation with Complex 1B. Following the above procedureyielded 7.3 g of polyethylene, corresponding to an activity of 1460mmol⁻¹h⁻¹bar⁻¹.

EXAMPLE 4 Propylene polymerisation with Complex 1B

The polymerisation was started by addition of Complex 1B (2.5 μM in 10ml toluene) to 100 m) heptane containing MAO (1000 eq) and TIBAL (25 eq)under 2 bar propylene pressure at 0° C. The polymerisations were run for30 min and terminated by addition of 2M HCl (50 ml). The layers wereseparated and the organic fraction further washed with 2M HCl (2×30 ml),water (30 ml), dried (MgSO₄), filtered and the solvent removed to yieldpolypropylene that was dried under vacuum for 12 h. The yield of polymerwas 5.3 g corresponding to an activity of 2125 gmmol⁻¹h⁻¹bar⁻¹.

Notes on the Examples:

Ac=Acetate

MAO=Methyl aluminoxane

TIBAL=Tri isobutylaluminium

EXAMPLE 5

Synthesis of 1-tert-butyl-2-methoxymethoxybenzene (Compound “5.1”)

See Note #1

The following reaction was carried out in an efficient fume cupboard. Toa solution of 2-tert-butylphenol (322 g, 2.1 moles) dissolved in 1.5litres of degassed HPLC grade thf (tetrahydrofuran) in a flask fittedwith an efficient condenser was added chunks of sodium (52 g, excess)and the reaction mix allowed to react for 3 hours then refluxedovernight to complete the reaction. A solution of MOMCl was formed in a3 litre, 3 neck flask fitted with an efficient double surfacedcondenser, pressure equalizing dropping funnel and a nitrogen inlet in awater bath at RT by the slow addition of AcCl (205 g, 2.6 moles) todimethoxymethane (229 g, 3.0 moles) with a catalytic amount of ZnCl₂ (2g). Caution MOMCl is a known carcinogen and the reaction is exothermic!!After addition of the AcCl the reaction mixture is stirred for 30minutes and the dropping funnel replaced with a septum. The thf solutionof sodium phenolate added by cannula and the reaction mix stirred for 1hour to complete the reaction. The reaction minx is deactivated by theaddition of 500 mls of 2 M NaOH solution and stirring for a further 60minutes to decompose excess MOMCl. Ether (500 mls) is added and thephases separated. The organic phase was washed with 3×500 mls ofdistilled water and dried over MgSO₄, filtered and the ether removed ona Rota-Vap. The unreacted phenol was removed by passage through a basicalumina column using hexane as elutriation solvent. The recoveredmaterial (compound “5.1”) was purified by flash distillation underreduced pressure, 67-68° C. 0.4 mm Hg. Yield 287 g (74%). ¹H-NMR (250MHz, CDCl₃) δ 1.420(s, 9H, C(CH₃)₃), 3.519(s, 3H, OMe), 5.253(s, 2H,OCH₂O), 6.92-7.33(m, 4H, Ar—H).

Synthesis of (3-tert-Butyl-2-methoxymethoxyphenyl)phenylphosphineoxide(“compound 5.6”)

Reaction completed under N₂.

To a solution of PhPCl₂ (14.0 g, 78.2 mmole) in 200 mls of dry toluenewas added iPr₂NH (15.82 g, 21.9 mls, 156 mmole) and the slurry stirredovernight. The precipitated iPr₂NH.HCl was removed by filtration leavinga solution of “compound 5.4” in toluene. A slurry of “compound 5.2” wasformed by addition of BuLi (31.3 mls, 2.5 M, 78.2 mmole) to a solutionof “compound 5.1” (15.2 g, 78.2 mmole) in 100 mls of ether and stirringat RT overnight. The slurry of compound 5.2 was added to the toluenesolution of “compound 5.4” cooled to −78° C. and the solution allowed towarm to RT (room temperature) and stirred for 1 hour to generate“compound 5.5” in situ. The reaction was deactivated by addition of 100mls of distilled H₂O and 100 mls of 2 M HCl and stirring for 4 hours.The organic phase was separated, washed with 2×100 mls of distilledwater and dried over Na₂SO₄. The solvent was removed on a Roto-Vap. Thecrude product was purified by flash column chromatography with ether aselutriation solvent (R_(f)0.29 ether). Yield of a pale yellow oil 19.3 g(77.5%). ³¹P{¹H}-MNR (101 MHz, CDCl₃) δ 17.91 ppm.

Preparation of1,2-Ethanediylbis{(3-tert-Butyl-2-methoxymethoxyphenyl)phenylphosphineoxide} (“Compound 5.7”) see Note #2 below: Reaction completed under N₂

To a solution of “compound 5.6” (10.0 g, 31.42 mmole) in 50 mls of THFat −20° C. (ice/acetone) was added slowly BuLi (12.25 ml, 2.5 M, 30.63mmole) and the orange solution warmed to RT, reacted for 1 hour thencooled to −20° C. Ethylene glycol di-p-tosylate (5.56 g, 15.0 mmole) wasadded in lots over 15 minutes then the slurry warmed to RT, stirred for1 hour then refluxed for 2 hours. The reaction mix was cooled to roomtemperature and deactivated by addition of distilled H₂O. The productwas extracted with DCM (dichloromethane) and the combined DCM extractswere washed with 3×50 mls of H₂O and dried over Na₂SO₄. The DCM wasremoved under vacuum and the residue triturated with hexane overnight.The crude product was recovered by filtration. FW 662.75. Yield 45%.³¹P{¹H}-NMR (101 MHz, CDCl₃) 35.41 and 35.69 ppm. Crystals suitable forstructural determination were isolated from a benzene solution of“Compound 5.7” layered with hexane indicating the presence of a RS/SRdiasteriomeric pair. ³¹P{¹H}-NMR (101 MHz, CDCl₃) δ 35.69 ppm.

Preparation of1,2-Ethanediylbis{(3-tert-Butyl-2-hydroxyphenyl)phenylphosphine oxide}(“compound 5.8”)

A sample of “Compound 5.7” (6 g, 9.05 mmole) was dissolved in 50 mls ofHOAc and 5 mls of H₂O added. The reaction mix was heated to-reflux for 2hours, cooled and the product extracted with EtOAc, the extracts washedwith 50 mls H₂O dilute NH₃ then H₂O. The EtOAc layer was dried overNa₂SO₄, filtered and the solvent removed under vacuum. The residue wasextracted with MeOH at RT to leave an insoluble material and a secondfraction was recovered by cooling the MeOH solution to −78° C. Aseparate deprotection of “compound 5.7” (RS/SR) isolated from above leadto the MeOH insoluble product. FW 574.64. Yield (MeOH sol. RR/SS) 1.5 g(28.8%), ³¹P{¹H}-NMR (101 MHz, CDCl₃) δ 46.70 ppm. Yield (MeOH insol.RS/SR) 2.2 g (42.3%), ³¹P{¹H}-NMR (101 MHz, CDCl₃) δ 46.79 ppm.

Preparation of1,2-Ethanediylbis{(3-tert-Butyl-2-hydroxyphenyl)phenylphosphine}(“Compound 5.9”): Reaction completed under N₂

To a solution of “Compound 5.8”(RR/SS) (0.72 g, 1.25 mmole) in 5 ml ofthf was added AlH₃ [formed by the slow addition of conc. H₂SO₄ (0.613 g,0.33 ml, 6.25 mmole) to a slurry of LiAlH₄ (0.474 g, 12.5 mmole) in 50mls of thf, stirred overnight, allowed to settle and filtered] and thereaction mix heated to reflux for 2 hours, cooled and deactivated by theslow addition of HOAc, then H₂O. The product was recovered by extractioninto ether. The ether layer was washed with 3×50 mls of H₂O and driedover Na₂SO₄, filtered and dried under vacuum. Racemisation was observed.³¹P{¹H}-NMR (101 MHz, CDCl₃) δ −43.26 and δ −43.33 ppm. FW 542.64. Theproducts were isolated by extraction with MeOH to give MeOH insol.RS/SR, yield 0.28 g (41%) ³P{¹H}-NMR (101 MHz, CDCl₃) δ −43.33 ppm, andMeOH sol. RR/SS, yield 0.21 g (30.9%) ³¹P{¹H}-NMR (101 MHz, CDCl₃) δ−43.25 ppm. Assignments were made by partial reduction of “Compound 5.8”(RS/SR) to give mainly product at ³¹P{¹H}-NMR δ −43.33 while partialreduction of “compound 5.8” (RR/SS) gave mainly product at ³¹P{¹H}-NMR δ−43.25.

Notes

#1 Method of Hibbert, F.Spiers, K. J., Journal of the ChemicalSociety-Perkin Transactions 2, 1989, 377-380.

#2 Modified Method of Wife, R. L.; Vanoort, A. B.; Vandoorn, J. A.Vanleeuwen, P., Synthesis, 1983, 71-73.

EXAMPLE 6 Polymerisation of α-olefins using “[OPPO]VO(OPr)” ie theligand “compound 5.9” prepared in Example 5

Ethylene Poylmerisation. A Fischer-Porter Reactor was filled with dryheptane (200 ml) under a nitrogen atmosphere. The reactor was placedunder 2 bar ethylene pressure at room temperature and DMAC (1M inhexane) was added. Where used, ethyl trichloroacetate was also added.The catalyst was prepared by addition of a toluene solution ofVO(O^(n)Pr)₃ to a toluene solution of ligand “compound 5.9” (prepared inExample 5) (in a 1:1 molar ratio) and activated by addition of DMAC (30eq.) followed by stirring for 2 min. After stirring the reactor mixturefor 5 min, the catalyst was injected. The polymerisation was terminatedby addition of 2M HCl and MeOH and the polymer collected by filtration,washed with MeOH and dried at 60° C. under vacuum. DMAC is dimethylaluminium chloride. Run 1. Catalyst loading = 5.0 μmol DMAC = 0.85 mmolEthyl trichloroacetate = 0.0 mmol Run Time = 1 h Exotherm = 2.5° C.Polymer yield = 1.93 g Activity = 193 g/mmol · h · bar

Run 2. Catalyst loading = 5.0 μmol DMAC = 0.85 mmol Ethyltrichloroacetate = 1.0 mmol Run Time = 15 min Exotherm = 43° C. Polymeryield = 10.23 g Activity = 4092 g/mmol · h · bar

Run 3. Catalyst loading = 0.5 μmol DMAC = 0.99 mmol Ethyltrichloroacetate = 1.0 mmol Run Time = 1 h Exotherm = 3.2° C. Polymeryield = 0.72 g Activity = 720 g/mmol · h · bar

1-32. (canceled)
 33. A polymerisation catalyst comprising (1) transitionmetal complex having the following Formula A:

wherein the monovalent groups R¹ and R² are independently selected from—R^(a), —OR^(b), —NR^(c)R^(d), and —NHR^(e): the monovalent groupsR^(a), R^(b), R^(c), R^(d), and R^(e), and the divalent group R³ areindependently selected from (i) aliphatic hydrocarbon, (ii) alicyclichydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatichydrocarbon (v) heterocyclic groups and (vi) heterosubstitutedderivatives of said groups (i) to (v); M is a metal from Group 3 to 11of the Periodic Table or a lanthanide metal; E is phosphorus or arsenic;X is an anionic group, L is a neutral donor group; y and z areindependently zero or integers such that the number of X and L groupssatisfy the valency and oxidation state of the metal M, and (2) anactivator compound, with the proviso that (A) when M is vanadium, n=1 or2 and (B) when M is not vanadium n=2 and the R¹ groups on the two units

are linked to form R⁵ such that Formula A becomes Formula B.

and wherein the divalent group R⁵ is selected from the divalent groups—R^(a′)—, —O—R^(b′)—, —O—R^(b′)—O—, —N—(R^(c))R^(d′—, —N(R) ^(c))—,—N(R^(c))R^(d′—N(R) ^(c)) —, —Si(R^(c))₂—R^(a′)—Si(R^(c))₂—, and—Si(R^(c))₂—; the divalent groups R^(a′), R^(b′), and R^(d′) beingindependently selected from divalent (i) aliphatic hydrocarbon, (ii)alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkylsubstituted aromatic hydrocarbon (v) heterocyclic groups and (vi)heterosubstituted derivatives of said groups (i) to (v).
 34. Apolymerisation catalyst as claimed in claim 33 wherein M is a Group 3 to7 transition metal.
 35. A polymerisation catalyst as claimed in claim 34wherein M is a Group 3 to 6 transition metal.
 36. A polymerisationcatalyst as claimed in claim 33 wherein M is titanium, vanadium orchromium.
 37. A polymerisation catalyst as claimed in claim 33 wherein Mis vanadium.
 38. A polymerisation catalyst as claimed in claim 33wherein E is phosphorus.
 39. A polymerisation catalyst as claimed inclaim 33 wherein the anionic group X is selected from halide, ahydrocarbyl group, a carboxylate, an oxide, an amide, an alkoxide; anacetylacetonate, a hydroxyl and a non-coordinating orweakly-coordinating anion selected from tetrafluoroborate, a fluorinatedaryl borate and a triflate.
 40. A polymerisation catalyst as claimed inclaim 33 wherein the anionic groups X are monoanionic, dianionic ortrianionic.
 41. A polymerisation catalyst as claimed in claim 33 whereinthe neutral donor group L is selected from a solvate molecule, an amine,a phosphine, an olefin, water or a conjugated or nonconjugated diene.42. A polymerisation catalyst compound as claimed in claim 33 having aformula selected from:


43. A polymerisation catalyst as claimed in claim 42 wherein thetransition metal complex is the Formula B compound.
 44. A polymerisationcatalyst as claimed in claim 33 wherein the activator compound isselected from organoaluminium compounds and organoboron compounds.
 45. Apolymerisation catalyst as claimed in claim 44 wherein the activatorcompound is selected from trimethylaluminium, triethylaluminium,tributylaluminium, tri-n-octylaluminium, ethylaluminium dichloride,diethylaluminium chloride, methylaluminium dichloride, dimethylaluminiumchloride, tris(pentafluorophenyl) aluminium, alumoxanes,dimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate,triphenylboron, dimethylphenylammonium tetra(pentafluorophenyl)borate,sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate,H⁺(OEt₂)[(bis-3,5-trifluoromethyl)phenyl]borate,trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl) boron.46. A polymerisation catalyst as claimed in claim 33 wherein theoptional activator is provided by a Lewis acid selected from (a)ionic-bonding compounds having a CdCl₂ type or a CdI₂ type of layeredcrystal structure; (b) clays, clay minerals, or ion-exchange layeredcompounds; (c) heteropoly-compounds; and (d) halogenated lanthanoidcompounds.
 47. A polymerisation catalyst as claimed in claim 33 whereinthere is present a promoter comprising a halogenated organic compound.48. A polymerisation catalyst system as claimed in claim 47 wherein thepromoter is selected from carbon tetrachloride, hexachloroethylene,benzylbromide, benzylchloride, ethyl trichloroacetate and 2,3- or1,3-dichloropropylene, chloroform (CHCl₃) and n-butylchloride.
 49. Apolymerisation catalyst as claimed in claim 33 wherein the catalyst ison a support material selected from silica, alumina, zirconia, magnesia,magnesium chloride, a polymer or prepolymer.
 50. A polymerisationcatalyst as claimed in claim 33 wherein in addition to the definedcatalyst there is present one or more other catalysts for polymerising1-olefins.
 51. A polymerisation catalyst as claimed in claim 50 whereinthe one or more other catalysts for polymerising 1-olefins are selectedfrom Ziegler-Natta catalyst systems, metallocene-based catalysts, orheat activated supported chromium oxide catalysts.
 52. A process for thepolymerisation and copolymerisation of 1-olefins, cyclooelifins ordienes comprising contacting the monomeric olefin under polymerisationconditions with the polymerisation catalyst claimed in claim
 33. 53. Aprocess as claimed in claim 52 wherein the process is for thehomopolymerisation of 1-olefins and wherein the monomer is selected fromethylene, propylene, butene, hexene, and styrene.
 54. A process asclaimed in claim 52 wherein the process is for the copolymerisation of1-olefins and wherein the monomer is selected from ethylene, propylene,1-butene, 1-hexene, 4-methylpentene-1, 1-octene, methyl methacrylate,methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate, vinylchloride, styrene, butadiene, hexadiene and norbornene.
 55. A process asclaimed in claim 52 comprising the copolymerisation of ethylene and orpropylene with comonomers selected from 1-butene, 1-hexene,4-methylpentene-1, methyl methacrylate, methyl acrylate, butyl acrylate,acrylonitrile, vinyl acetate, and styrene, diene, cyclic olefin,norbornene and substituted norbornene.
 56. A process as claimed in claim52 wherein the process is carried out under gas phase, slurry phase orsolution phase polymerisation conditions.
 57. A process as claimed inclaim 52 wherein the process is carried in the presence of hydrogen gasto modify the average molecular weight of the produced polymer.
 58. Acompound having the formula

wherein R is tertiary butyl.
 59. A transition metal complex having thefollowing Formula A:

wherein the monovalent groups R¹ and R² are independently selected from—R^(a), —OR^(b), —NR^(c)R^(d), and —NHR^(e): the monovalent groupsR^(a), R^(b), R^(c), R^(d), and R^(e), and the divalent group R³ areindependently selected from (i) aliphatic hydrocarbon, (ii) alicyclichydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatichydrocarbon (v) heterocyclic groups and (vi) heterosubstitutedderivatives of said groups (i) to (v); M is a metal from Group 3 to 7 ofthe Periodic Table or a lanthanide metal; E is phosphorus or arsenic; Xis an anionic group, L is a neutral donor group; y and z areindependently zero or integers such that the number of X and L groupssatisfy the valency and oxidation state of the metal M, with the provisothat (A) when M is vanadium, n=1 or 2 and (B) when M is not vanadium n=2and the R¹ groups on the two units

are linked to form R⁵ such that Formula A becomes Formula B.

and wherein the divalent group R⁵ is selected from the divalent groups—R^(a′)—, —O—R^(b′)—, —O—R^(b′)—O—, —N—(R^(c))R^(d′)—, —N(R^(c))—,—N(R^(c))—R^(d′)—N(R^(c))—, —Si(R^(c))₂—R^(a′)—Si(R^(e))₂—, and—Si(R^(c))₂—; the divalent groups R^(a′), R^(b′), and R^(d′) beingindependently selected from divalent (i) alphatic hydrocarbon, (ii)alicylic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substitutedaromatic hydrocarbon (v) heterocyclic groups and (vi) heterosubstitutedderivatives of said groups (i) to (v).
 60. A complex as claimed in claim59 wherein M is a Group 3 to 6 transition metal.
 61. A complex asclaimed in claim 59 wherein. M is titanium, vanadium or chromium.
 62. Acomplex as claimed in claim 59 wherein M is vanadium.
 63. A complex asclaimed in claim 59 wherein E is phosphorus.
 64. A complex as claimed inclaim 59 wherein the anionic group X is selected from halide, ahydrocarbyl group, a carboxylate, an oxide, an amide, an alkoxide; anacetylacetonate, a hydroxyl and a non-coordinating orweakly-coordinating anion selected from tetrafluoroborate, a fluorinatedaryl borate and a triflate.
 65. A complex as claimed in claim 59 whereinthe anionic groups X are monanionic, dianionic or trianionic.
 66. Acomplex having a formula selected from: